Roof sheeting or roof flashing

ABSTRACT

A composition comprising 100 parts of an elastomer selected from the group consisting of EPDM, butyl rubber and a EPDM-butyl rubber mixture; 0.1 to 3.0 parts of a compound having the structural formula [(CH 2 ) n  NCS] 2  S 6 , where n is 4 or 5; and 0 to 0.5 parts of a sulfur donor curative is disclosed. The composition has particular application as roof sheeting or flashing.

This is a continuation of U.S. patent application, Ser. No. 600,250,filed Apr. 16, 1984, now U.S. Pat. No. 4,514,442, which in turn is adivision of U.S. patent application, Ser. No. 381,259, filed May 24,1982, now U.S. Pat. No. 4,461,875, which in turn is acontinuation-in-part of U.S. patent application, Ser. No. 363,325, filedMar. 29, 1982, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The instant invention is directed to an elastomeric composition selectedfrom the group consisting of ethylene-propylene-non-conjugated dieneterpolymer (EPDM), isobutylene-conjugated diene copolymer (butyl rubber)and mixtures of the terpolymer and copolymer. More particularly, theinstant invention is directed to an elastomeric composition selectedfrom the group consisting of ethylene-propylene-non-conjugated dieneterpolymer, isobutylene conjugated diene copolymer and mixtures of theterpolymer and copolymer which may be applied to a roof as roofingsheets or flashing members which, upon exposure to ambient influences,have the ability to crosslink.

2. Background of the Prior Art

Elastomeric ethylene-propylene-non-conjugated diene terpolymer (EPDM)and isobutylene-conjugated diene copolymer (butyl rubber) compositionsare well known in the art. The use of EPDM and butyl rubber compositionsas the material of construction of roof sheeting is also known in theart. Such sheeting, provided in the cured, or crosslinked, state provideexcellent materials for use on a roof in those applications where flatmaterial is acceptable for disposition on equally flat or moderatelycontoured roofing structures. However, when the crosslinked EPDM orbutyl rubber sheeting of the prior art is disposed on intricatelycontoured surfaces of a roof, such as parapet, chimney, ventilatorsections and the like, the flat crosslinked sheeting of the prior art isnot acceptable. That is, crosslinked EPDM or butyl rubber lacks theformability to successfully and permanently follow, cover and retainirregular shaped contours.

Roofing material used to follow irregular contours is known as flashing.Crosslinked EPDM or butyl rubber roof sheeting is not normally used asflashing because gaps readily develop around the contours between thesheeting sections of the roof, and those other portions of the roof inwhich the EPDM or butyl rubber is employed as flashing.

Whereas crosslinked EPDM or butyl rubber sheeting have each establishedexcellent reputations as effective barriers to roof leaks on thesurfaces upon which they are applied, still, this protection has notbeen available to those portions of the roof which are characterized bytheir irregular shape. Thus, the excellent protection afforded by EPDMor butyl rubber compositions has not been available as flashing. Thisresults in the inability to protect those section of the roofcharacterized by irregular shape against leakage. The utilization ofEPDM or butyl rubber roof sheeting, a most effective long term protectoragainst water leakage, is seriously compromised by this defect in curedEPDM and butyl rubber.

SUMMARY OF THE INVENTION

It has now been found that compositions selected from the groupconsisting of EPDM, butyl rubber and mixtures thereof may be applied toroofs, even those having highly contoured surfaces, lending the sameprotection to irregular shaped sections as that provided to flat sectionof a roof by cross-linked EPDM and butyl rubber sheeting. This isaccomplished by providing EPDM, butyl rubber or a mixture of EPDM andbutyl rubber which is flexible and formable and thus able to followintricate roof contours. This unique flexible EPDM, butyl rubber orEPDM-butyl rubber roofing composition is supplied in the uncured state.Uncured EPDM, butyl rubber or EPDM-butyl rubber mixture does not possesselasticity, a characteristic of these compositions in the crosslinkedstate. This permits the EPDM, butyl rubber or EPDM-butyl rubber mixtureto be formed around odd shapes and corners to effectively seal theseareas. The novel property provided by the new EPDM, butyl rubber orEPDM-butyl rubber mixture composition of this invention is the abilityto self-cure under ambient conditions.

In accordance with the instant invention, a composition is providedwhich comprises 100 parts of a elastomer selected from the groupconsisting of ethylene-propylene-non-conjugated diene terpolymer (EPDM)isobutylene-conjugated diene copolymer (butyl rubber) and a mixture ofEPDM and butyl rubber; 0.1 to 3.0 parts of a compound having thestructural formula [(CH₂)_(n) NCS]₂ S₆, where n is 4 or 5; and from 0 to5.0 parts of a sulfur donor curative, the compound having the structuralformula [(CH₂)_(n) NCS]₂ S₆ and the sulfur donor curative providing atleast 0.25 parts of total available sulfur, wherein all of the partsrecited are by weight.

DETAILED DESCRIPTION

The composition of this invention comprises an elastomer selected fromthe group consisting of ethylene-propylene-non-conjugated terpolymer(EPDM), isobutylene-conjugated diene copolymer (butyl rubber) and amixture of EPDM and butyl rubber, present with a compound having thestructural formula [(CH₂)_(n) NCS]₂ S₆, where n is 4 or 5 and,optionally, with a sulfur donor curative.

The compound having the structural formula [(CH₂)_(n) NCS]₂ S₆ where nis 4 or 5 is present in the composition in a concentration of 0.1 to 3.0parts by weight based on 100 parts by weight of elastomer. Morepreferably, the concentration of this compound, a hexasulfide, per 100parts by weight of elastomer, is in the range of between 0.2 and 2.0parts by weight. Most preferably, the concentration of hexasulfide isbetween 0.3 and 1.2 parts by weight per 100 parts by weight ofelastomer. In a preferred embodiment the compound having the structuralformula [(CH₂)_(n) NCS]₂ S₆ is dipentamethylenethiuram hexasulfide.

The sulfur donor curative, which, if present, contributes with thehexasulfide to provide the minimum necessary total available sulfurrequired in this composition, 0.25 parts per 100 parts of elastomer, maybe one or more of the following sulfur donating compounds: sulfur;dimethyl-diphenylthiuram disulfide; dipentamethylenethiuramtetrasulfide; tetraethylthiuram disulfide; tetramethylthiuram disulfide;alkyl disulfides; selenium diethyldithiocarbamate; seleniumdimethyldithiocarbamate; 4,4'-dithiodimorpholine; andN,N'-dithiobis(hexahydro-2H-azepinon-2). It should be appreciated thatthis list is not exclusive and other sulfur donating compounds, known inthe art, are within the contemplation of this invention.

In some embodiments, within the scope of this invention, one or moreadditional vulcanizing accelerators may be included in the compositionof this invention. These accelerators are distinguished from the twoabove described constituents in that these additional accelerators donot have sulfur donor capability. Among the classes of acceleratorscontemplated for incorporation, alone or in combination with one or moreadditional accelerators, in the composition of this invention are:dialkylthiourea; trialkylthiourea; tetraalkylthiourea;2-mercaptoimidazoline; N,N'-diphenylquanidine;N,N-di(2-methylphenyl)quanidine; salts of dialkyldithiocarbamates,wherein the alkyl groups may have from 1 to 6 carbon atoms and the saltsmay be formed with bismuth, cadmium, copper, iron, lead, potassium,selenium, sodium, tellurium, zinc, or mono-alkylamines;dialkylenethiuram monosulfides and tetraalkylenethiuram monosulfides,where the alkylene or alkyl groups have from 1 to 8 carbon atoms;mercaptobenzothiazole, 4-morpholinylbenzothiazyl disulfide and zincmercaptobenzothiazole.

Although any of the above recited compounds may be employed, alone or incombination, in the composition of this invention, sulfur is especiallypreferred as the sulfur donating curative of this invention.

The concentration of the sulfur donor curative ranges from 0 to 5.0parts by weight per 100 parts of elastomer. In a more preferredembodiment, the curative is present in an amount of 0.4 to 3.0 parts andstill more preferably the curative concentration is 0.5 to 2.0 parts,where the parts recited are by weight per 100 parts by weight ofelastomer.

In one preferred embodiment EPDM is used as the elastomer in thecomposition of this invention. The EPDM used is a terpolymer ofethylene, one or more olefin monomer(s) having the general formula H₂C═CHR, where R is an alkyl group having from 1 to 7 carbon atoms. In apreferred embodiment this olefin is propylene. The EPDM also includes anon-conjugated diene which may be a C₆ -C₁₂ linear or C₉ -C₁₀ bridgedring hydrocarbon diene copolymerizable with the aforementioned monomers.The most commonly employed non-conjugated dienes in the terpolymer ofthis invention are 1,4-hexadiene, dicyclopentadiene and5-ethylidene-2-norbornene.

In another preferred embodiment the elastomer of the composition of thisinvention is butyl rubber. The butyl rubber of this invention isisobutylene-conjugated diene copolymer comprising from 1 to 10% byweight of conjugated diene. Among the dienes within the contemplation ofthis invention are 2-methyl-1,3-butadiene; 1,3 butadiene; and2,3-dimethylbutadiene-1,3. Of these 2-methyl-1,3-butadiene is mostpreferred.

In yet another preferred embodiment the elastomer is a mixture of EPDMand butyl rubber, where the EPDM and butyl rubber has the meanings givenin the above two paragraphs. There is no limitation on the relativeamounts of the two constituents in that either component alone producesthe novel result obtained in this invention.

It is within the contemplation of this invention that additionalingredients may be incorporated into the composition of this invention.Among the additives that can be present in this composition areprocessing oils, plasticizers and filler and reinforcing agents. Amongthe filler and reinforcing agents especially useful in the compositionof this invention are carbon black, silicates, talc, clay, calciumcarbonate and the like.

The compounding of the composition of this invention may be accomplishedby any suitable means including an internal mixer, a transfer mixer, anextruder or an open mill. Independent of the method of compounding thecomposition, the resulting composition has a cure rate which correlateswith the development of crosslinking.

In a preferred embodiment of this invention a roofing composition isprovided, which comprises the composition of this invention. The roofingcomposition may be in the form of sheets of the desired dimensions,usually formed by calendering or extruding the sheet, then cutting thesheet to proper size and shape. The sheets may be cut for use as roofsheeting or flashing members.

When used as a roof covering, the composition of this invention maycover any roofing base material, such as wood, composition board,concrete, brick or metal. In many applications, insulating or vaporbarrier layers may be first placed over the roof bottom prior to thedisposition of the composition of this invention. It is emphasized,however, that such layers are not essential to the carrying out of thisinvention.

Another aspect of this invention is a method of protecting roofs fromwater leaks by disposition thereupon of the composition of thisinvention.

In another preferred embodiment the composition of this invention isemployed as a water liner. In this application sheets of the compositionare employed as a reservoir liner, a pond liner and the like.

The composition and method of this invention may be better understood inconjunction with the following examples. These examples illustrative ofthe scope of the instant invention, are given by way of illustration andshould not be construed as limiting the invention in any way.

EXAMPLE 1

A general "master batch" was prepared by adding 331/3 parts by weight ofEPDM to a type "B" laboratory Banbury [trademark] internal mixer set at77 revolutions per minute. To this was added 125 parts by weight ofcarbon black (high structure HAF type N-347); 95 parts by weight ofextender oil (paraffinic petroleum oil, SUS at 37.8° C.: 2642); 50 partsby weight of magnesium silicate (Mistron Vapor [trademark], particlesize equal to or less than 6 microns); 5 parts by weight zinc oxide and1 part by weight of stearic acid. To this was added 662/3 parts byweight of EPDM. Thus, the EPDM constituent comprised 100 parts by weightof the composition. After the remaining EPDM was added the ram waslowered. Mixing for one minute followed at which time the temperaturereached 115° C. The ram was then raised, the ram and throat of the mixerwere swept, and the ram was again lowered. Mixing continued for anadditional 90 seconds at which time the compound temperature reached138° C. The mixer was stopped, the ram was raised, and the master batchwas dropped on a mill to cool.

Five compositions were prepared employing the above master batch. TheEPDM uncured rubber, comprising 100 parts of the 376 parts by weight ofthe master batch, included a blend of 50 parts of a terpolymer noted as"EPDM I." EPDM I is a terpolymer containing 51.9% ethylene, 39.1%propylene and 9.0% 5-ethylidene-2-norborene, all percentages being byweight. EPDM I had a Mooney viscosity (ML-1 plus 4) at 125° C. of 68.The remaining 50 parts by weight of EPDM was a terpolymer denoted as"EPDM II." EPDM II is a terpolymer containing 71.6% ethylene, 23.9%propylene and 4.5% 5-ethylidene-2-norbornene, said percentages based onthe total weight of the terpolymer. EPDM II had a Mooney viscosity (ML-1plus 4) at 125° C. of 77.

Five samples, Samples Nos. 1-5, were prepared from these fivecompositions, whose preparation is described above. Each sample, asstated above, included 376 parts by weight of the master batch,comprising 100 parts by weight of EPDM, the exact constituency of whichis recited above. To the master batch was added dipentamethylenethiuramhexasulfide (DPTH) and sulfur, the concentrations of which aresummarized in Table I below.

The mixture of the master batch, DPTH and sulfur were formed intosamples by banding the mixture on the back roll of a 20.32×40.64 cm millat a preset temperature of 95° C. (front roll) and 65° C. (back roll).The nip between the rolls was adjusted to provide a 2.03 mm sheet, whilemaintaining about 2 cm rolling bank of compound. After 30 seconds, airfree sheet was cut from the mill and dusted with mica for easierhandling.

For testing purposes, six 7.62×15.24 cm samples were cut from the dustedsheet and hung in an air circulating oven. From both the unaged and agedsamples standard Dumbbell Die A were cut according to ASTM D-412.Tensile strength at break, measured in megaPascals, and elongation atbreak, measured in percent, measurements were made using an Instron[trademark] tester Model LTD, and the measured results were calculatedin accordance with ASTM D-412. All testing was carried out at 23° C.

In addition to strength testing, the curing characteristics of thesamples were investigated using a Monsanto Rheometer [trademark], modelMPV, at 3° arc, 15 Hz, square die. The curing characteristics arereported as the increase in torque, measured in Newton meters, betweenthe minimum value and the value obtained after 60 minutes at 100°.

                                      TABLE 1                                     __________________________________________________________________________                    Sample No.                                                                    1    2    3     4     5                                       __________________________________________________________________________    Constituents,                                                                 in parts by Weight                                                            Master Batch    376  376  376   376   376                                     DPTH            0.1  0.3  0.6   1.2   2.4                                     Sulfur          0.5  0.5  0.5   0.5   0.5                                     Physical Properties                                                           Torque (60), cN.m                                                                             1.13 5.65 9.04  11.3  13.56                                   Unaged* Tensile Strength at                                                                   3.65 3.65 3.65  3.65  3.65                                    Break, MPa                                                                    Aged** Tensile Strength at                                                                    4.83 6.0  8.0   12.1  16.6                                    Break, MPa                                                                    Change in Tensile Strengh %                                                                   +32  +64  +119  +230  +355                                    Unaged Elongation at Break,* %                                                                640  640  640   640   640                                     Aged Elongation at Break,** %                                                                 340  370  380   380   390                                     Change in % Elongation, %                                                                     -47  -42  -41   -41   -39                                     __________________________________________________________________________     *Master batch, not including DPTH or sulfur                                   **28 days at 70° C. in a circulating air oven                     

The results of these tests clearly indicate that even under mild agingconditions, 70° C., a temperature readily encountered on the roof of abuilding, compositions within the contemplation of this inventionsurprisingly develop a state of cure from satisfactory to excellentdepending on the concentration of the hexasulfide of this invention, inthis example DPTH, and, optionally, the sulfur donating curative, inthis example, sulfur.

EXAMPLE 2

Four samples were prepared using the master batch of Example 1, that is,a master batch which included a blend of 50 parts EPDM I and 50 partsEPDM II in combination with a varying amount of DPTH, a constant amountof sulfur and one additional accelerator, zincO,O-di-n-butylphosphorodithioate (ZBPD). A summary of the constituentsof these compositions, Samples 6-9, and the results of physical testing,as described in Example 1, employing these four samples, are tabulatedin Table II.

                  TABLE II                                                        ______________________________________                                                       Sample No.                                                                    6     7       8       9                                        ______________________________________                                        Constituents                                                                  in parts by Weight,                                                           Master Batch     376     376     376   376                                    DPTH             0.1     0.3     0.6   1.2                                    ZBPD             1.5     1.5     1.5   1.5                                    Sulfur           0.5     0.5     0.5   0.5                                    Physical Properties                                                           Torque (60), cN.m                                                                              1.13    6.78    15.82 31.64                                  Tensile Strength, MPa, unaged                                                                  3.65    3.65    3.65  3.65                                   Tensile Strength, MPa, aged*                                                                   6.14    8.83    12.20 15.32                                  Elongation, % aged*                                                                            380     420     430   430                                    ______________________________________                                         *28 days at 70° C., air circulating oven                          

The results of these tests, summarized in Table II, demonstrate the cureefficiency of compositions containing DPTH, at relatively low curativeconcentrations, ZBPD and sulfur.

EXAMPLE 3

Additional master batch concentrates were prepared in accordance withthe procedure enumerated in Example 1. However, different blends of EPDMwere employed. That is, the relative concentrations of ethylene andpropylene were changed. In addition, the termonomer was also varied.Thus, samples using dicyclopentadiene (DCPD) and 1,4-hexadiene (HXD)were employed in the samples of Example 3, as well as samples using thediene of Examples 1 and B 2,5-ethylidene-2-norbornene (ENB).

Six compositions, denoted as Samples 10-15, were prepared from themaster batches in which the concentration of the DPTH, and sulfur, weremaintained at a constant level of 0.4 parts and 0.5 parts, respectively,by weight per 100 parts EPDM. These samples included additionalaccelerators within the contemplation of this invention. Theconcentration of these accelerators was maintained constant in all thecompositions of this example.

Table III below summarizes and defines the six compositions produced. Inaddition, these samples were tested in accordance with the proceduresset forth in Example 1.

                                      TABLE III                                   __________________________________________________________________________                   Sample No.                                                                    10    11    12    13    14    15                               __________________________________________________________________________    EPDM: No.      III   IV    V     VI    VII   VIII                             Ethylene, %    64.6  64.6  64.9  51.0  54.3  53.6                             Propylene, %   30.4  30.4  30.6  47.0  42.6  40.4                             Termonomer, type                                                                             DCPD  DCPD  ENB   ENB   HXD   HXD                              Termonomer, %  5.0   5.0   4.5   2.0   3.1   6.0                              ML-1 plus 4, @ 100° C.                                                                49    85    62    65    70    74                               Constituents, Parts by Weight                                                 EPDM           100   200.sup.(1)                                                                         100   100   100   100                              N-347 Carbon Black                                                                           125   125   125   125   125   125                              Extender oil   75    --.sup.(1)                                                                          85    80    85    85                               Mineral filler.sup.(2)                                                                       50    50    50    50    50    50                               Stearic Acid   1.0   1.0   1.0   1.0   1.0   1.0                              Zinc oxide     5.0   5.0   5.0   5.0   5.0   5.0                              DPTH           0.4   0.4   0.4   0.4   0.4   0.4                              MBT.sup.(3)    0.4   0.4   0.4   0.4   0.4   0.4                              ZDDC.sup.(4)   0.4   0.4   0.4   0.4   0.4   0.4                              ZDBP.sup.(5)   1.5   1.5   1.5   1.5   1.5   1.5                              Sulfur         0.5   0.5   0.5   0.5   0.5   0.5                              Physical Properties                                                           Torque (60).sup.(6), cN · m                                                         6.78  15.82 28.25 25.96 9.04  28.25                            Tensile Strength, original, MPa                                                              0.64  3.61  1.18  0.70  0.92  0.47                             Tensile Strength, aged.sup.(7)                                                               3.03  8.69  8.07  3.24  5.52  8.89                             Tensile Strength change, %                                                                   +373  +141  +584  +363  +500  +1791                            Elongation, % original                                                                       370   460   490   400   700   560                              __________________________________________________________________________     .sup.(1) EPDM contained 100 pts extender oil, no additional oil was           introduced.                                                                   .sup.(2) Magnesium silicate, particle size 6 micron or less.                  .sup.(3) Mercaptobenzothiazole.                                               .sup.(4) Zinc dimethyldithiocarbamate.                                        .sup.(5) Zinc O,O--din-butylphosphorodithioate.                               .sup.(6) Rheometer test at 100° C.; increase in torque between         minimum value and 60 minutes value.                                           .sup.(7) Aged 28 days at 70° C., air circulating oven.            

The data in Table III establishes that compositions within thecontemplation of this invention provide excellent cure development evenwhen employing a variety of EPDM's and a combination of DPTH and otheraccelerators.

EXAMPLE 4

Roof sheeting samples were prepared by formulating three additionalcompositions, Samples 16-18. These samples were aged, both in an aircirculating oven and outdoors on a roof in Naugatuck, Conn. Table IVsummarizes the composition of the roof sheeting samples of this example,as well as the results of the physical tests to which these samples wereput, after aging in an air oven and on a roof.

                  TABLE IV                                                        ______________________________________                                                        Sample No.                                                                    16     17       18                                            ______________________________________                                        Constituents, parts by wt.                                                    EPDM, No.         IV       V        IX.sup.(1)                                EPDM, amount      200      100      140                                       N-346 Carbon Black                                                                              125      125      125                                       Mineral filler.sup.(2)                                                                          50       50       50                                        Extender oil.sup.(3)                                                                            10       85       55                                        Zinc oxide        5.       5.       5.                                        Stearic acid      1.       1.       1.                                        DPTH              0.3      0.3      0.3                                       MBT               0.3      0.3      0.3                                       ZDDC              0.3      0.3      0.3                                       ZDBP              1.5      1.5      1.5                                       Sulfur            0.5      0.5      0.5                                       Physical Properties                                                           Original Tensile Strength, MPa                                                                  1.72     1.06     6.63                                      Original Elongation, %                                                                          300      440      540                                       Torque (60), cN.m.sup.(4)                                                                       3.39     18.08    24.86                                     Aged 28 days at 70° C.                                                 Tensile Strength, MPa                                                                           5.38     6.90     11.45                                     Tensile Strength change, %                                                                      213      552      73                                        Elongation, %     440      420      430                                       Aged 1 month, roof                                                            Tensile Strength, MPa                                                                           2.14     3.79     8.83                                      Tensile Strength, change, %                                                                     24       257      33                                        Elongation, %     340      390      420                                       Aged 3 months, roof                                                           Tensile Strength, MPa                                                                           2.53     5.03     10.0                                      Tensile Strength change, %                                                                      47       375      51                                        Elongation, %     370      360      390                                       ______________________________________                                         .sup.(1) EPDMIX: E(71.6) P(23.9)ENB(4.5%) terpolymer containing oil (40       pph); ML1 plus 4 at 100°  C. = 55.                                     .sup.(2) and .sup.(3) as in Example 1.                                        .sup.(4) Rheometer test at 100° C.; increase in torque between         minimum value and 60 minute value.                                       

Example 4 establishes the practicality of employing the compositions ofthis invention as roof sheeting or flashing, not only by testing aftersimulated aging in an air circulating oven, but also after actual roofexposure aging.

EXAMPLE 5

Five additional samples, samples 19-23, were prepared to determine theeffectiveness of compositions which comprise butyl rubber or EPDM-butylrubber mixtures as the elastomer. It is noted that sample 19, whichemploys EPDM as the sole elastomer, is included for comparison purposes.

All the samples were prepared from a "master batch" in accordance withthe procedure of Example 1. Of course, the master batches for eachsample were appropriately modified to incorporate the properconcentration of butyl rubber in samples 20-23.

To these master batch samples was added additional additives whoseconcentration are summarized in Table V.

These samples were tested to obtain their torque characteristic. Asstated above, torque is an indicia of the composition's curingcharacteristic. The torque of the samples tested is also tabulated inTable V.

                  TABLE V                                                         ______________________________________                                                   Sample No.                                                                    19    20      21      22    23                                     ______________________________________                                        Constituents,                                                                 Parts by Weight                                                               EPDM I       50.0    37.5    25.0  12.5  --                                   EPDM II      50.0    37.5    25.0  12.5  --                                   Butyl Rubber --      25.0    50.0  75.0  100                                  N-346 Carbon Black                                                                         120     115     110   105   100                                  Extender Oil 85      80      75    70    65                                   Mineral Filler                                                                             50      45      40    35    30                                   MBT          0.6     0.6     0.6   0.6   0.6                                  ZDDC         0.6     0.6     0.6   0.6   0.6                                  ZBPD         1.5     1.5     1.5   1.5   1.5                                  DPTH         0.6     0.6     0.6   0.6   0.6                                  Sulfur       0.5     0.5     0.5   0.5   0.5                                  Physical Property                                                             Torque (60) cN.m                                                                           40.7    42.5    44.2  45.1  45.1                                 ______________________________________                                         Note: All symbols as defined or described in previous examples.          

This example illustrates the effectiveness of samples using butyl rubberor EPDM-butyl rubber samples as the elastomer. Samples incorporatingbutyl rubber alone or in combination with EPDM all have curingcharacteristics slightly superior to the good curing property exhibitedby EPDM.

The detailed description and examples given above are provided toillustrate the scope and spirit of the instant invention. Theseemodiments and examples will suggest to others, skilled in the art,other embodiments and examples within the scope of this invention. Suchembodiments and examples are within the contemplation of this invention.Therefore, the scope of this invention should be limited only by theappended claims.

What is claimed is:
 1. A method of protecting a roof against water leakscomprising:(a) providing a self-curing, flexible and formablecomposition comprising:(i) 100 parts of an elastomer selected from thegroup consisting of EPDM, butyl rubber and mixtures thereof; (ii) 0.1 to3.0 parts of a compound having the structural formula: [(CH₂)_(n) NCS]₂S₆, where n is 4 or 5; and (iii) 0 to 5.0 parts of a sulfur donorcurative;wherein said components (ii) and (iii) provide at least 0.25part of total available sulfur, all parts being by weight; and whereinsaid composition exhibits an increase in torque between the minimumvalue and the value obtained after 60 minutes at 100° C. of at leastabout 15 cNm; and (b) disposing said composition upon at least a portionof said roof.
 2. The method of claim 1, wherein said compositionexhibits an increase in torque of at least about 31 cNm.
 3. The methodof claim 1, wherein the composition comprises from 0.4 to 5.0 parts of asulfur donor curative.
 4. The method of claim 1, wherein the compositioncomprises from 0.4 to 3.0 parts of compound (ii) and 0.2 to 2.0 parts ofthe sulfur donor curative (iii).
 5. The method of claim 1, wherein thecomposition is disposed as a single layer roofing or flashing sheet. 6.The method of claim 1 wherein the component (ii) isdipentamethylenethiuram hexasulfide.
 7. The method of claim 1, whereinsaid composition upon exposure to a temperature of 70° C. for 28 days ina circulating hot air oven attains an increase in tensile strength of atleast 141 percent.
 8. A method of protecting a roof against water leakscomprising:(a) providing a self-curing, flexible and formablecomposition comprising:(i) 100 parts of an EPDM elastomer; (ii) 0.1 to3.0 parts of a compound having the structural formula: [(CH₂)_(n) NCS]₂S₆, where n is 4 or 5; and (iii) 0 to 5.0 parts of a sulfur donorcurative;wherein said components (ii) and (iii) provide at least 0.25part of total available sulfur, all parts being by weight; and whereinsaid composition exhibits an increase in torque between the minimumvalue and the value obtained after 60 minutes at 100° C. of at leastabout 15 cNm; and (b) disposing said composition upon at least a portionof said roof.
 9. A method of claim 8, wherein said composition exhibitsan increas in torque of at least about 31 cNm.
 10. The method of claim8, wherein the composition comprises from 0.4 to 5.0 parts of a sulfurdonor curative.
 11. The method of claim 8, wherein the compositioncomprises from 0.4 to 3.0 parts of compound (ii) and 0.2 to 2.0 parts ofthe sulfur donor curative (iii).
 12. The method of claim 8, wherein thecomposition is disposed as a single layer roofing or flashing sheet. 13.The method of claim 8, wherein the component (ii) isdipentamethylenethiuram hexasulfide.
 14. A method of protecting a roofagainst water leaks comprising:(a) providing a self-curing, flexible andformable composition comprising:(i) 100 parts of a butyl rubberelastomer; (ii) 0.1 to 3.0 parts of a compound having the structuralformula: [(CH₂)_(n) NCS]₂ S₆, where n is 4 or 5; and (iii) 0 to 5.0parts of a sulfur donor curative;wherein said components (ii) and (iii)provide at least 0.25 part of total available sulfur, all parts being byweight; and wherein said composition exhibits an increase in torquebetween the minimum value and the value obtained after 60 minutes at100° C. of at least about 15 cNm; and (b) disposing said compositionupon at least a portion of said roof.
 15. The method of claim 14,wherein said composition exhibits an increase in torque of at leastabout 31 cNm.
 16. The method of claim 14, wherein the compositioncomprises from 0.4 to 5.0 parts of a sulfur donor curative.
 17. Themethod of claim 14, wherein the composition comprises from 0.4 to 3.0parts of compound (ii) and 0.2 to 2.0 parts of the sulfur donor curative(iii).
 18. The method of claim 14, wherein the composition is disposedas a single layer roofing or flashing sheet.
 19. The method of claim 14,wherein the component (ii) is dipentamethylenethiuram hexasulfide.
 20. Amethod of protecting a roof against water leaks comprising:(a) providinga self-curing, flexible and formable composition comprising:(i) 100parts of EPDM and butyl rubber elastomeric mixture; (ii) 0.1 to 3.0parts of a compound having the structural formula: [(CH₂)_(n) NCS]₂ S₆,where n is 4 or 5; and (iii) 0 to 5.0 parts of a sulfur donorcurative;wherein said components (ii) and (iii) provide at least 0.25part of total available sulfur, all parts being by weight; and whereinsaid composition exhibits an increase in torque between the minimumvalue and the value obtained after 60 minutes at 100° C. of at leastabout 15 cNm; and (b) disposing said composition upon at least a portionof said roof.
 21. A method of claim 20, wherein said compositionexhibits an increase in torque of at least about 31 cNm.
 22. The methodof claim 20, wherein the composition comprises from 0.4 to 5.0 parts ofa sulfur donor curative.
 23. The method of claim 20, wherein thecomposition comprises from 0.4 to 3.0 parts of compound (ii) and 0.2 to2.0 parts of the sulfur donor curative (iii).
 24. The method of claim20, wherein the composition is disposed as a single layer roofing orflashing sheet.
 25. The method of claim 20, wherein the component (ii)is dipentamethylenethiuram hexasulfide.
 26. A roof having disposedthereon a self-curing, flexible and formable composition comprising:(i)100 parts of an elastomer selected from the group consisting of EPDM,butyl rubber and mixtures thereof; (ii) 0.1 to 3.0 parts of a compoundhaving the structural formula [(CH₂)_(n) NCS]₂ S₆, where n is 4 or 5;and (iii) 0 to 5.0 parts of a sulfur donor curative; wherein saidcomponents (b) and (c) provide at least 0.25 part of total availablesulfur, all parts being by weight.
 27. The roof of claim 26, whereinsaid composition upon exposure to a temperature of 70° C. for 28 days ina circulating hot air oven attains an increase in tensile strength of atleast 32 percent.
 28. The roof of claim 26, wherein the component (ii)of the composition is dipentamethylenethiuram hexasulfide.
 29. A roofhaving disposed thereon a self-curing, flexible and formable compositioncomprising:(i) 100 parts of an EPDM elastomer; (ii) 0.1 to 3.0 parts ofa compound having the structural formula [(CH₂)_(n) NCS]₂ S₆, where n is4 or 5; and (iii) 0 to 5.0 parts of a sulfur donor curative; whereinsaid components (b) and (c) provide at least 0.25 part of totalavailable sulfur, all parts being by weight.
 30. The roof of claim 29,wherein said composition upon exposure to a temperature of 70° C. for 28days in a circulating hot air oven attains an increase in tensilestrength of at least 32 percent.
 31. The roof of claim 29, wherein thecomponent (ii) of the composition is dipentamethylenethiuramhexasulfide.
 32. A roof having disposed thereon a self-curing, flexibleand formable composition comprising:(i) 100 parts of a butyl rubberelastomer; (ii) 0.1 to 3.0 parts of a compound having the structuralformula [(CH₂)_(n) NCS]₂ S₆, where n is 4 or 5; and (iii) 0 to 5.0 partsof a sulfur donor curative; wherein said components (b) and (c) provideat least 0.25 part of total available sulfur, all parts being by weight.33. The roof of claim 32, wherein said composition upon exposure to atemperature of 70° C. for 28 days in a circulating hot air oven attainsan increase in tensile strength of at leat 32 percent.
 34. The roof ofclaim 32, wherein the component (ii) of the composition isdipentamethylenethiuram hexasulfide.
 35. A roof having disposed thereona self-curing, flexible and formable composition comprising:(i) 100parts of an EPDM, butyl rubber elastomer mixture; (ii) 0.1 to 3.0 partsof a compound having the structural formula [(CH₂)_(n) NCS]₂ S₆, where nis 4 or 5; and (iii) 0 to 5.0 parts of a sulfur donor curative; whereinsaid components (b) and (c) provide at least 0.25 part of totalavailable sulfur, all parts being by weight.
 36. The roof of claim 35,wherein said composition upon exposure to a temperature of 70° C. for 28days in a circulating hot air oven attains an increase in tensilestrength of at leat 32 percent.
 37. The roof of claim 35, wherein thecomponent (ii) of the composition is dipentamethylenethiuramhexasulfide.
 38. A roof sheeting or roof flashing comprising:(i) 100parts of an elastomer selected from the group consisting ofethylene-propylene-non-conjugated diene terpolymer, butyl rubber andmixtures thereof; (iii) 0.1 to 3.0 parts of a compound having thestructural formula [(CH₂)_(n) NCS]₂ S₆, where n is 4 or 5; and (iii) 0to 5.0 parts of a sulfur donor curative; wherein said components (b) and(c) provide at least 0.25 part of total available sulfur, all partsbeing by weight.
 39. The roof sheeting or roof flashing of claim 38,wherein the component (ii) is dipentamethylenethiuram hexasulfide.